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Geological and Inorganic Materials F. E. Lichte, J. L. Seeley,* L. L. Jackson, D. M. McKown, and J. E. Taggart, Jr.
U S . Geological Survey, P.O. Box 25046, Denver Federal Center, Denver, Colorado 80225
The current review covers the literature reported from November 1984 to October 1986. This review covers the analytical techniques that are currently applied to the analysis of geological and inorganic materials. We have tried to
highlight work either that applies state of the art techniques to novel problems or that has advanced the state of the art which should open new doors in the fields of geological or inorganic analysis. Other reviews encompass the theoretical
This article not subject to US. Copyright. Published 1987 by the American Chemical Society
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GEOLOGICAL AND INORGANIC MATERIALS
aspects of the techniques which are applied to these subjects, and therefore, unless these developments appear to offer significantly new capabilities, we have not attempted to include these studies. We find it necessary to restrict the references cited because of the huge volume of literature. For this relatively short period of 2 years, a key words search of Chemical Abstracts listed over 2600 references in these fields that are appropriate for inclusion in this review. In addition to Chemical Abstracts, several journals were manually surveyed. Moore ( 1 ) and Moore and Canapa ( 2 , 3 )have written the past three reviews for this journal. They deserve a great deal of credit for a job well done. In addition to the general technique review, they also reviewed in more detail specific subjects of current interest. This review will follow a similar organizational structure. Obviously, the specific topics chosen will be different. While Moore included the rare-earth elements (REE) in a separate section, and REE determinations continue to be of interest, the analytical methodologies are now quite well developed and no longer warrant a special section. Inductively coupled plasma mass spectrometry (ICP-MS) is perhaps the newest and most exciting technique to be developed in this field in the past 10 years and only now are we beginning to see publications dealing with its application to geological and inorganic materials. Therefore, this review article will include ICP-MS.
DC ARC EMISSION SPECTROSCOPY The application of optical emission spectrography (Le., dc arc) to the direct analysis of geochemical materials has been reported extensively over the past 4 decades. It is not surprising, therefore, that most of the more recent publications encompass novel methods of elemental separation/preconcentration prior to arc excitation and photometric measurement. A paper by Matusiewicz (4)described the combination of an electrochemical method for preconcentration and separation with emission spectrographic analysis for the determination of trace metals in samples of high salt content. Detection limits were reported in the 0.1-5 ng g range for 13 elements, including Bi, Cd, Mo, Pb, Sb, and 1. Ryspekova and Azimova ( 5 ) reported detection limits of 10 ng/g for the Pt-group metals in ultrabasic rocks using a chemical separation technique followed by emission spectrographic analysis. Yu and Xie (6)combined ion-exchange separation with optical emission spectrometry for the determination of 15 trace rare-earth elements in rock. Detection limits ranged from 1 to 700 ng/g. Han (7)used an emission spectrographic method for the determination of Ag, Sn, and B in geologic materials a t detection limits of 0.03, 1,and 3 pg/g, respectively.
4
ATOMIC ABSORPTION SPECTROPHOTOMETRY Atomic absorption spectrometric detection is currently being applied extensively in three modes: flame atomization, graphite furnace atomization, and atom cells for hydride generation. Each of these categories can be broken down into novel areas for sample preparation, separation, or measurement. Flame atomic absorption spectrophotometry (FAAS) remains a widely used method, and the major instrument manufacturers have published “cookbooks” for all of the elements. Either air/acetylene or NzO/acetylene flames are used depending on the element. Terashima (8)has reviewed the use of AAS for the determination of trace constituents in rocks and minerals. Methods of analysis for ore-grade material and concentrates were reported for W and Sn. Raoot et al. (9) determined W by FAAS. In their method, the sample was fused with NazC03 and W was separated from iron by precipitation. Potassium persulfate was used as a releasing agent to improve sensitivity. Their reported accuracy was within
